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Publication numberUS6703455 B1
Publication typeGrant
Application numberUS 09/762,482
PCT numberPCT/FI1999/000657
Publication dateMar 9, 2004
Filing dateAug 9, 1999
Priority dateAug 7, 1998
Fee statusPaid
Also published asCN1133663C, CN1317022A, DE69911626D1, DE69911626T2, EP1109842A1, EP1109842B1, EP1109842B9, US6706655, US20010008869, WO2000008073A1
Publication number09762482, 762482, PCT/1999/657, PCT/FI/1999/000657, PCT/FI/1999/00657, PCT/FI/99/000657, PCT/FI/99/00657, PCT/FI1999/000657, PCT/FI1999/00657, PCT/FI1999000657, PCT/FI199900657, PCT/FI99/000657, PCT/FI99/00657, PCT/FI99000657, PCT/FI9900657, US 6703455 B1, US 6703455B1, US-B1-6703455, US6703455 B1, US6703455B1
InventorsThomas Garoff, Timo Leinonen, Sirpa Ala-Huikku
Original AssigneeW. R. Grace & Co.-Conn
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Catalyst component comprising magnesium, titanium, a halogen and an electron donor, its preparation and use
US 6703455 B1
Abstract
A process for the preparation of an olefin polymerization catalyst component containing a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di- oligo- or polyester as internal electron donors is disclosed. A catalyst component and its use for the polymerization of α-olefins such as propene are also disclosed.
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Claims(69)
What is claimed is:
1. A process for the preparation of an olefin polymerization catalyst component comprising a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di-, oligo- or polyester as internal electron donor ED, comprising the steps of:
(i) providing a magnesium compound (ab) containing an alkoxy moiety, selected from the group consisting of a magnesium dialkoxide, a complex containing a magnesium dihalide and an alcohol, and a complex containing a magnesium dihalide and a magnesium dialkoxide, and
(ii) reacting said magnesium compound (ab) with at least one dicarboxylic acid dihalide (c) which forms said dicarboxylic acid di-, oligo- or polyester as internal donor ED and has the formula (1):
wherein each R″ is a similar or different C1-C20 hydrocarbyl group or both R″:s form together with the two unsaturated carbons of the formula a C5-C20 aliphatic or aromatic ring, and X′ is a halogen, to give an intermediate (abc),
(iii) reacting said intermediate (abc) with at least one titanium tetrahalide TiX″4 (d) wherein X″ is a halogen,
(iv) recovering said catalyst component in crude form or recovering a precursor of said catalyst component, and
(v) optionally washing said crude catalyst component or said precursor, to give said catalyst component, and
by adding and reacting in connection with the above step (ii) or (iii) at least one reactive halogenated hydrocarbon (e) of the formula (2)
R′″(X′″)n  (2)
wherein R′″ is an n-valent C1-C20 hydrocarbyl group, X′″ is a halogen and n is an integer selected from 1, 2, 3 and 4 and wherein said reactive halogenated hydrocarbon (e) is added in an amount corresponding to a molar ratio Mgtotal added/(e) of between 1:0.2 and 1:20.
2. A process according to claim 1, wherein at least one of steps (i) to (iii), are performed in solution with optional stirring and/or heat.
3. A process according to claim 2, wherein in step (iv), said catalyst component is recovered by precipitation.
4. A process according to claim 1, 2 or 3, wherein in said reactive halogenated hydrocarbon (e) of formula (2), R′″ is a mono or bivalent C1-C10 hydrocarbyl group, X′″ is chlorine and n is 1 or 2.
5. A process according to claim 1, wherein said reactive halogenated hydrocarbon (e) is added in an amount corresponding to a molar ratio Mgtotal added/(e) of between about 1:1 and about 1:4.
6. A process according to claim 1, wherein said magnesium compound (ab) containing an alkoxy moiety is provided by reacting at least one magnesium compound precursor (a), selected from the group consisting of a dialkyl magnesium R2Mg, an alkyl magnesium alkoxide, wherein each R is a similar or different C1-C20 alkyl, and a magnesium dihalide MgX2, wherein X is a halogen with at least one alcohol (b), selected from the group consisting of monohydric alcohols R′OH and polyhydric alcohols R′ (OH)m, wherein R′ is an 1-valent or, respectively, an m-valent C1-C20 hydrocarbyl group and m is an integer selected from 2, 3, 4, 5 and 6, to give said magnesium compound (ab).
7. A process according to claim 1, wherein said magnesium compound precursor (a) is a dialkyl magnesium R2Mg, in which each R is a similar or different C4-C12 alkyl group.
8. A process according to claim 1, wherein said magnesium compound precursor (a) is a magnesium dihalide, which is magnesium dichloride.
9. A process according to claim 1, wherein said magnesium compound (ab) is provided by reacting, in any order, a dialkyl magnesium R2Mg and a magnesium dihalide MgX2 with at least one alcohol (b), selected from the consisting of monohydric alcohols R′OH and polyhydric alcohols R′ (OH)m, wherein R′ is an 1-valent or, respectively, an m-valent C1-C20 hydrocarbyl group and m is an integer selected from 2, 3, 4, 5 and 6.
10. A process according to claim 1, wherein said alcohol (b) is a monohydric alcohol R′OH in which R′ is a C2-C16 alkyl group.
11. A process according to claim 1, wherein said magnesium compound (a) is in step (i) reacted with said alcohol (b) which is said monohydric alcohol R′OH, in a molar ratio Mg/ROH of between 1:4 and 1:1.
12. A process according to claim 1, wherein said alcohol (b) is a polyhydric alcohol R′ (OH)m, wherein R′ is a di, tri or tetravalent C2-C16 alkyl group and m is an integer selected from 2, 3 and 4.
13. A process according to claim 1, wherein in step (i), said magnesium compound precursor (a) is reacted with said alcohol (b) which is said polyhydric alcohol R′ (OH)m in a molar ratio Mg/R′(OH)m of between 1:1 and 1:0.25.
14. A process according to claim 1, wherein in step (i), said magnesium compound precursor (a) is reacted with at least two of said alcohols (b), one of which is said monohydric alcohol R′OH and the other of which is said polyhydric alcohol R′ (OH)m.
15. A process according to claim 1, wherein in step (i), said magnesium compound precursor (a) is reacted with said at least one alcohol (b), under at least one of the following conditions:
at a temperature, of about 30 C. to about 80 C.,
for a period of about 10 min to about 90 min
in the presence of a C5-C10 hydrocarbon solvent.
16. A process according to claim 1, wherein in said dicarboxylic acid dihalide (c) of the formula (1), both R″:s form together with the two unsaturated carbons of said formula (1) a C5-C20 aliphatic or a C6-C20 aromatic ring, and X′ is chlorine, preferably that said dicarboxylic acid dihalide (c) is phthaloyl dichloride.
17. A process according to claim 1, wherein in step (ii), said magnesium compound (ab) is reacted with said dicarboxylic acid dihalide (c) in a molar ratio Mgtotal added/(c) between 1:1 and 1:0.1.
18. A process according to claim 1, wherein in step (ii), said magnesium compound (ab) is reacted with said dicarboxylic acid dihalide (c), under at least one of the following conditions:
adding said dicarboxylic acid dihalide (c) under room temperature and heating the obtained reaction mixture,
keeping the reactants together at a temperature of about 30 C. to about 80 C.,
keeping the reactants together for a period of about 10 min to about 90 min,
reacting the reactants in the presence of a C5-C10 hydrocarbon solvent.
19. A process according to claim 18, wherein after said magnesium compound (ab) has been reacted with said dicarboxylic acid dihalide (c), said C5-C10 hydrocarbon solvent is removed by evaporation.
20. A process according to claim 19, wherein after said C5-C10 hydrocarbon solvent has been removed by evaporation, said second intermediate (abc) is contacted with said reactive halogenated hydrocarbon (e) for a period of about 10 min to about 90 min.
21. A process according to claim 20, wherein after said intermediate (abc) has been contacted with said reactive halogenated hydrocarbon (e), a dissolving C5-C10 hydrocarbon is added.
22. A process according to claim 1, wherein said titanium tetrahalide (d) is titanium tetrachloride.
23. A process according to claim 1, wherein in step (iii), said intermediate (abc) is reacted with said titanium tetrahalide (d) in a molar ratio Mgtotal added/(d) between 1:100 and 1:1.
24. A process according to claim 1, wherein, in step (iii), said intermediate (abc) is added slowly to said titanium tetrahalide (d) to form a solution of said catalyst component.
25. A process according to claim 21 and 24, wherein said toluene solution of said intermediate (abc) is added dropwise to said titanium tetrahalide (d) at 110 C.
26. A process according to claim 25, wherein of said intermediate (abc) is reacted with said titanium tetrahalide (d) at 110 C. for about 5 min to about 20 min.
27. A process according to claim 1, wherein in step (iv), said catalyst component in crude form or a precursor thereof is recovered by cooling a solution of said catalyst component for the precipitation of said crude catalyst component or said precursor thereof and preferably allowing it to settle.
28. A process according to claim 27, wherein immediately before said precipitation, a C5-C10 hydrocarbon solvent is added to said catalyst component solution.
29. A process according to claim 27 or 28, wherein after said crude catalyst component or said precursor thereof has settled, the supernatant liquid is removed by decantering or siphoning.
30. A process according to claim 1, wherein in step (v), said recovered crude catalyst component or said precursor thereof is washed with toluene.
31. A process according to claim 1, wherein in step (v), said recovered crude catalyst component or said precursor thereof is washed with heptane.
32. A process according to claim 1, wherein in step (v), said recovered crude catalyst component or precursor thereof is washed with pentane.
33. A process according to claim 1, wherein in step (v) said recovered crude catalyst component or precursor thereof is washed to give the following ratio of said magnesium dihalide, said titanium tetrahalide, and said dicarboxylic acid di-, oligo- or polyester as internal electron donor ED (3):
(MgX2)8-10(TiX″4)1(ED)0.7-1.3  (3)
wherein MgX2 is said magnesium dihalide, TiX″4 is said titanium tetrahalide and ED is said dicarboxylic acid di-, oligo- or polyester as internal electron donor whereby said recovered catalyst component is washed first with toluene then at least twice with hot (90) heptane, and finally with pentane.
34. A process according to claim 1, wherein the washed catalyst component is dried.
35. An olefin polymerization catalyst component comprising a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di-, oligo- or polyester as internal electron donor ED, wherein it has been prepared according to the process of claim 1.
36. A catalyst component according to claim 34, wherein it contains halogen from about 10% to about 60% more than the amount of halogen calculated on the basis of the amounts of magnesium and titanium present, assuming that all of the magnesium is in the form of said MgX2 and all of the titanium is in the form of said TiX4, wherein X is a halogen.
37. A catalyst component according to claim 35, wherein it is essentially homogenous and has the following ratio of said magnesium dihalide, said titanium tetrahalide, and said dicarboxylic acid di-, oligo- or polyester as internal electron donor ED (3):
(MgX2)8-10(TiX″4)1(ED)0.7-1.3  (3)
wherein MgX2 is said magnesium dihalide, TiX″4 is said titanium tetrahalide, X and/or X″ is Cl and ED is said dicarboxylic acid di-, oligo- or polyester as internal electron donor, and contains halogen from about 10% to about 60% more than the amount of halogen calculated on the basis of the amounts of magnesium and titanium present, assuming that all of the magnesium is in the form of said MgX2 and all of the titanium is in the form of said TiX4, wherein X is a halogen.
38. A catalyst component according to claim 35, 36 or 37, wherein it shows a X-ray diffraction pattern with a lamellar thickness indicating a peak at 17 2Θ, showing a clear position shift compared to normal amorphous MgCl2 which gives a height indicating peak at 15 2Θ.
39. Process for the polymerization of olefins, by comprising the steps of
(A) preparing a catalyst component according to claim 1
(B) feeding to a polymerization reactor said catalyst component, as well as a cocatalyst, which has the formula (4)
RpAlrX3r-p  (4)
wherein R is a C1-C10 alkyl, X is a halogen, p is an integer from 1 to (3r−1), and r is 1 or 2, the molar ratio between said catalyst component and said cocatalyst, expressed as Al/Ti, being 10-2000
optionally an external electron donor,
optionally a C4-C10 hydrocarbon solvent,
optionally a chain transfer agent, which is hydrogen, and
at least one olefin monomer,
(C) carrying out the polymerization of said olefin monomer in said polymerization reactor to give an olefin polymer (=homopolymer or copolymer) and
(D) recovering said olefin polymer.
40. Process according to claim 39, wherein said catalyst component is prepared by the process of claim 1.
41. Process according to claim 39 or 40, comprising the steps of
(A) providing a solid olefin polymerization catalyst component which is essentially homogenous and comprises a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di-, oligo- or polyester as internal electron donor ED in the following ratio (3):
(MgX2)8-10(TiX″4)1(ED)0.7-1.3  (3)
wherein MgX2 is said magnesium dihalide, TiX″4 is said titanium tetrahalide, X and/or X″ is Cl, and ED is said dicarboxylic acid di-, oligo- or polyester as internal donor, and contains halogen from about 10% to about 60% more than the amount of halogen calculated on the basis of the amounts of magnesium and titanium present, assuming that all of the magnesium is in the form of said MgX2 and all of the titanium is in the form of said TiX4, wherein X is a halogen.
42. The process according to claim 2, wherein all of steps (i) to (iii) are performed in solution with optional stirring and/or heat.
43. The process of claim 42, wherein several hydrocarbon solvents are used.
44. The process according to claim 4, wherein said reactive halogenated hydrocarbon (e) is a butyl chloride or (1,4)-dichlorobutane.
45. The process according to claim 44, wherein said reactive halogenated hydrocarbon (e) is tertiary butyl chloride or (1,4)-dichlorobutane.
46. The process according to claim 7, wherein the R groups are different and one R is a butyl group and the other R is an octyl group.
47. The process according to claim 10, wherein R′ is a C4-C12 alkyl group.
48. The process according to claim 10, wherein (b) is 2-ethyl-1-hexanol.
49. The process according to claim 11, wherein the molar ratio Mg/ROH is between about 1:2.5 and about 1:1.5.
50. The process according to claim 12, wherein said alcohol (b) is a polyhydric alcohol selected from the group consisting of ethylene glycol, 2-butyl-2-ethyl-1,3-propanediol and glycerol.
51. The process according to claim 13, wherein in step (i), said magnesium compound precursor (a) is reacted with said alcohol (b) which is said polyhydric alcohol R′ (OH)m in a molar ratio Mg/R′(OH)m of between about 1:0.8 and about 1:0.3.
52. The process according to claim 17, wherein in step (ii), said magnesium compound (ab) is reacted with said dicarboxylic acid dihalide (c) in a molar ratio Mgtotal added/(c) between about 1:0.6 and about 1:0.25.
53. The process according to claim 19, wherein after said magnesium compound (ab) has been reacted with said dicarboxylic acid dihalide (c), said C5-C10 hydrocarbon solvent is removed by evaporation at about 100 C. to about 110 C.
54. The process according to claim 21, wherein the C5-C10 hydrocarbon is toluene, and a molar ratio Mgtotal added/toluene is between about 1:2 and about 1:10.
55. The process according to claim 23, wherein in step (iii), said intermediate (abc) is reacted with said titanium tetrahalide (d) in a molar ratio Mgtotal added/(d) between about 1:50 and about 1:5.
56. The process according to claim 24, wherein, in step (iii), said intermediate (abc) is added dropwise to said titanium tetrahalide (d), which is hot, to form a solution of said catalyst component.
57. The process according to claim 28, wherein immediately before said precipitation, toluene in a molar ratio Mgtotal added/toluene of about 1:10 to about 1:100 is added to said catalyst component solution.
58. The process according to claim 33, wherein ED is a di-, oligo- or polyester phthalic acid.
59. The process according to claim 34, wherein the washed catalyst component is dried by evaporation.
60. The process according to claim 39, wherein R is a C1-C4 alkyl.
61. The process according to claim 60, wherein R is ethyl.
62. The process according to claim 39, wherein X is chlorine.
63. The process according to claim 39, wherein the molar ratio between said catalyst component and said cocatalyst, expressed as Al/Ti is 200-500.
64. The process according to claim 39, wherein the external electron donor is a silane.
65. The process according to claim 64, wherein the external electron donor is a C1-C12 alkyl-C1-C12 alkoxy silane.
66. The process according to claim 65, wherein the external electron donor is cyclohexyl methyl dimethoxy silane.
67. The process according to claim 39, wherein the C4-C10 hydrocarbon solvent is pentane, hexane and/or heptane.
68. The process according to claim 39, wherein the olefin monomer, is propene.
69. The process according to claim 41, wherein ED is a di-, oligo- or polyester phthalic acid.
Description

This application is the national phase under 35 U.S.C. 371 of PCT International Application No. PCT/FI99/00657 which has an International filing date of Aug. 9, 1999, which designated the United States of America.

The invention relates to a process for the preparation of an olefin polymerization catalyst component comprising a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di-, oligo- or polyester as internal electron donor. The invention also relates to such a catalyst component and its use for the polymerization of α-olefins such as propene.

BACKGROUND OF THE INVENTION

Generally, so called Ziegler-Natta catalyst components of the above kind have been prepared by reacting a magnesium halide-alcohol complex support with a titanium tetrahalide and an electron donor which usually is a phthalic acid di- oligo- or polyester. The preparation involves the use of large amounts of reagents and washing liquids, which are difficult to handle. Additionally, byproducts are formed, which cannot easily be regenerated or destroyed, but form an environmental problem.

For example, the preparation of a conventional polypropene catalyst component involves the reaction of a magnesium dichloride-alcohol complex support with titanium tetrachloride to give a surface layer of reactive β-magnesium dichloride as intermediate and hydrogen chloride and titanium alkoxy trichloride as byproducts. Then, the surface layer of reactive β-magnesium dichloride intermediate is activated with further titanium tetrachloride and optionally an internal electron donor to give said catalyst component (the treatment with a titanium halide such as titanium tetrachloride is henceforth called titanation). The result is an essentially inert magnesiumchloride based support covered with active sites based on titanium, chlorine and the optional internal electron donor.

The titanium alkoxy trichloride byproduct formed in such a titanation is a catalyst poison and must be carefully removed by extensive washing using large amounts of titanium tetrachloride. Further, the titanium alkoxy trichloride must be carefully separated from the titanium tetrachloride washing liquid, if the latter is to be reused e.g. for activating the reactive β-magnesium dichloride. Finally, the titanium alkoxy trichloride is a hazardous waste material, which is difficult to dispose of.

Thus, in a typical propene polymerization catalyst component preparation involving two titanations and three heptane washes, one mol of produced catalyst component (mol Mg) requires about 40 mol of titanium tetrachloride e.g. as washing liquid to be circulated, and produces as waste material an amount of about three mol of titanium alkoxy trichloride as well as about three mol of hydrogen chloride.

Sumitomo, EP 0 748 820 A1 (hereinafter referred to as “Sumitomo”), has prepared dialkoxy magnesium, reacted it with titanium tetrachloride to form an intermediate and then reacted the intermediate with phthalic acid dichloride to form a catalytically active propene polymerization catalyst component. The activity was raised by repeated titanations, as well as repeated washes with toluene and hexane. See page 10, lines 14 to 37, of said publication.

Said process of Sumitomo has avoided the reaction between the magnesium dichloride-alcohol complex and titanium tetrachloride, and thereby eliminated the formation of large amounts of catalytically poisonous titanium alkoxy trichloride byproduct. However, as much as four titanations and hydrocarbon treatments are still needed to give satisfactory catalytic activity.

DESCRIPTION OF THE INVENTION

The purpose of the present invention is to provide a process which results in a catalyst component having satisfactory activity without producing harmful byproducts such as said titanium alkoxy trichloride or requiring the use of large amounts of titanation reagent and/or washing liquid.

The problem described above has now been solved with a novel process for the preparation of a catalyst component of the above type, which is mainly characterized by the steps of:

(i) providing a magnesium compound (ab) containing an alkoxy moiety, selected from the group consisting of a magnesium dialkoxide, a complex containing a magnesium dihalide and an alcohol, and a complex containing a magnesium dihalide and a magnesium dialkoxide, and

(ii) reacting said magnesium compound (ab) with at least one dicarboxylic acid dihalide (c) which forms said dicarboxylic acid di-, oligo- or polyester as internal donor ED and has the formula (1):

wherein each R″ is a similar or different C1-C20 hydrocarbyl group or both R″:s form together with the two unsaturated carbons of the formula a C5-C20 aliphatic or aromatic ring, and X′ is a halogen, to give an intermediate (abc), and

(iii) reacting said intermediate (abc) with at least one titanium tetrahalide TiX″4 (d) wherein X″ is a halogen,

(iv) recovering said catalyst component in crude form or recovering a precursor of said catalyst component, and

(v) optionally washing said crude catalyst component or said precursor, to give said catalyst component, and

by adding and reacting in connection with the e step (ii) or (iii) at least one halogenated hydrocarbon (e) of the formula (2)

R′″(X′″)n  (2)

wherein R′″ is an n-valent C1-C20 hydrocarbyl group, X′″ is a halogen and n is an integer selected from 1, 2, 3 and 4.

It has thus been found that a high activity olefin polymerization catalyst comprising a magnesium halide, a titanium tetrahalide and a dicarboxylic acid di-, oligo- or polyester as internal donor can be prepared without the above mentioned disadvantages by reacting a magnesium compound containing an alkoxy moiety with a dicarboxylic acid dihalide and a titanium tetrahalide and adding a reactive halogenated hydrocarbon.

Of the above mentioned steps (i) to (iii) preferably all are performed in solution. For dissolution of the reactants, one or several hydrocarbon solvents can be used, optionally together with the application of stirring and/or heating. Performing the process in a solution means that all reagent molecules can react with each other, thus forming a homogenous reaction product. Earlier processes which have been performed by reacting a solid support with a titanium compound and an electron donor, see above, do not form homogenous reaction products.

The catalyst component is in step (iv) preferably recovered in solid form by precipitation. Precipitation in the present invention means that the reaction product formed in solution is recovered as a powder, the particles of which consist of similar molecules of that reaction product. The particles formed according to the present invention are thus homogenous, while the particles of earlier processes are more or less heterogenous (inert core+active surface).

It is preferable if said first and second intermediates as well as the final product of the claimed process are separate compounds with an essentially stoichiometric composition. Often, they are complexes. A complex is, according to Rompps Chemie-Lexicon, 7. Edition, Franckh'sche Verlagshandlung, W. Keller & Co., Stuttgart, 1973, page 1831, “a derived name of compounds of higher order, which originate from the combination of molecules,—unlike compounds of first order, in the creation of which atoms participate.

Reactive halogenated hydrocarbons (e) of the present invention are, e.g., monochloromethane, dichloromethane, trichloromethane (chloroform), tetrachloromethane, monochloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2,3-trichloropropane, 1-chlorobutane, 2-chlorobutane, isobutyl chloride, tert.butyl chloride, 1,4-dichlorobutane, 1-chloropentane and 1,5-dichloropentane, as well as their corresponding compounds having other halogens. The chlorinated hydrocarbons of the invention may also be unsaturated, provided that the unsaturation does not act as catalyst poison in the final catalyst component.

In the invention, it was found that the addition of a reactive halogenated hydrocarbon (e) during the process led to a significantly improved catalytic activity. In said reactive halogenated hydrocarbon (e) having the above formula (2), X′″ is preferably chlorine.

R′″ is preferably a mono- or bivalent saturated C1-C10 hydrocarbyl group. Preferably said reactive halogenated hydrocarbon (e) is a butyl chloride (BuCl) or a dichloroalkane like 1,4-dichlorobutane, more preferably tertiary butyl chloride or a dichloroalkane like 1,4-dichlorobutane, most preferably a dichloroalkane like 1,4-dichlorobutane.

It was also found, that especially good results were obtained, if said reactive halogenated hydrocarbon (e) is added in an amount corresponding to a molar ratio Mgtotal added/(e) of between 1:0.2 and 1:20, preferably between about 1:1 and about 1:4.

Said reactive halogenated hydrocarbon (e) can be added in step (ii) or (iii). Preferably it is added in connection with step (ii). This means that in the process, it is preferably added immediately before the dicarboxylic acid dihalide (c), together with it or immediately after it. As there is a possibility that the reactive halogenated hydrocarbon (e) may disturb the conversion of the dicarboxyl di-halide into said dicarboxylic acid di-, oligo- or polyester donor, it is most preferably added immediately after the addition of the dicarboxylic acid dihalide (c). The symbols (ab) and (abc) may include the added or reacted reactive halogenated hydrocarbon (e). The symbols do not limit the reactants leading to the corresponding intermediates to (a), (b), (c) and (d).

The process according to the present invention starts with step (i), in which said magnesium compound (ab) containing an alkoxy moiety is provided. According to one embodiment, said complex of said magnesium dihalide and said magnesium dialkoxide as said magnesium compound (ab) is preferably a magnesium dichloride-magnesium alkoxide complex having the formula MgCl2.[Mg(OR)2]t, wherein R is a C1-C20 alkyl or a C7-C27 aralkyl, preferably a C6-C16 alkyl, and t is 1-6, preferably about 2. It is e.g. prepared by reacting magnesium dichloride MgCl2 with an alcohol ROH into an intermediate which is a magnesium dichloride/alcohol complex MgCl2.(ROH)2t and reacting the magnesium dichloride-alcohol complex with t mol of a magnesium dialkyl MgR′″2, wherein R′″ is a hydrocarbyl group having 1 to 20 carbon atoms.

Preferably, the complex of said magnesium dihalide and a magnesium dialkoxide as said alkoxy compound is a magnesium dichloride-dimagnesium dialkoxide complex having the formula MgCl2.[Mg(OR)2]2, wherein R is a C1-C20 alkyl or a C7-C27 aralkyl, preferably a C6-C16 alkyl. The complex may e.g. be prepared by reacting magnesium dichloride with an alcohol ROH and the obtained intermediate with a dialkyl magnesium R′″2Mg essentially as follows:

 MgCl2+4ROH→MgCl2.4ROH

MgCl2.4ROH+2MgR′″2→MgCl2[Mg(OR)2]2+4R′″H

In the reaction between the magnesium dihalide, the alcohol and the dialkyl-magnesium, the molar ratio MgCl2:ROH is preferably 1:1 to 1:8, most preferably 1:2 to 1.5. The molar ratio MgCl2.4ROH:MgR′″2 is preferably 1:1 to 1:4, most preferably about 1:2. The temperature is preferably about 50 C. to about 150 C. and the reaction time preferably about 2 h to about 8 h. A hydrocarbon solvent such as toluene may be present in the reaction.

The magnesium compound (ab) is usually titaniumless. Most preferably, the magnesium compound (ab) is provided by reacting an alkyl magnesium compound and/or a magnesium dihalide with an alcohol. Thereby, at least one magnesium compound precursor (a), selected from the group consisting of a dialkyl magnesium R2Mg, an alkyl magnesium alkoxide RMgOR, wherein each R is a similar or different C1-C20 alkyl, and a magnesium dihalide MgX2, wherein X is a halogen, is reacted with at least one alcohol (b), selected from the group consisting of monohydric alcohols R′OH and polyhydric alcohols R′(OH)m, wherein R′ is an 1-valent or, respectively, an m-valent C1-C20 hydrocarbyl group and m is an integer selected from 2, 3, 4, 5 and 6, to give said magnesium compound (ab). R′ is the same or different in the formulas R′OH and R′(OH)m. By valence is understood the number of bonds that an atom can form (Stanley H. Pine, Organic Chemistry, 5. edition, McGraw-Hill, Inc., New York, 1987, page 10). The R of the dialkyl magnesium is preferably a similar or different C4-C12 alkyl. Typical magnesium alkyls are ethylbutyl magnesium, dibutyl magnesium, dipropyl magnesium, propylbutyl magnesium, dipentyl magnesium, butylpentylmagnesium, butyloctyl magnesium and dioctyl magnesium. Typical alkyl-alkoxy magnesium compounds are ethyl magnesium butoxide, magnesium dibutoxide, butyl magnesium pentoxide, magnesium dipentoxide, octyl magnesium butoxide and octyl magnesium octoxide. Most preferably, on R is a butyl group and the other R of R2Mg is an octyl group, i.e. the dialkyl magnesium compound is butyl octyl magnesium. When used as said magnesium compound precursor (a), the magnesium dihalide is preferably magnesium dichloride MgCl2.

The alcohol (b) of step (i) may be a monohydric alcohol, a polyhydric (by definition including dihydric and higher alcohols) alcohol or a mixture of at least one monohydric alcohol and at least one polyhydric alcohol. Magnesium enriched complexes can be obtained by replacing a part of the monohydric alcohol with the polyhydric alcohol.

Typical C1-C5 monohydric alcohols are methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, secbutanol, tert.butanol, n-amyl alcohol, iso-amyl alcohol, sec.amyl alcohol, tert.amyl alcohol, diethyl carbinol, akt. amyl alcohol, sec. isoamyl alcohol, tert.butyl carbinol. Typical C6-C10 monohydric alcohols are hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 4-heptanol, 2,4-dimethyl-3-pentanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 5-nonanol, diisobutyl carbinol, 1-decanol and 2,7-dimethyl-2-octanol. Typical >C10 monohydric alcohols are n-1-undecanol, n-1-dodecanol, n-1-tridecanol, n-1-tetradecanol, n-1-pentadecanol, n-1-hexadecanol, n-1-heptadecanol and n-1-octadecanol. The monohydric alcohols may be unsaturated, as long as they do not act as catalyst poisons. Preferable monohydric alcohols are those of formula R′OH in which R′ is a C2-C16 alkyl group, most preferably a C4-C12 alkyl group, like 2-ethyl-1-hexanol.

The amount of monohydric alcohol relative to the amount of magnesium compound precursor (a) may vary a lot, depending on the quality and quantity of the magnesium compounds, the dicarboxylic acid dihalide (c), the reactive halogenated hydrocarbon (e), is used and on whether the monohydric alcohol R′OH is used alone or in combination with a polyhydric alcohol R′(OH)m. The molar ratio Mg/R′OH is preferably between about 1:5 and about 1:1, more preferably between about 1:4 and about 1:1, most preferably between about 1:2.5 and about 1:1.5.

Typical polyhydric alcohols are ethylene glycol, propene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, pinacol, diethylene glycol, triethylene glycol, glycerol, trimethylol propane and pentaerythritol. According to one embodiment of the present invention, the polyhydric alcohol has the formula R′(OH)m, wherein R′ is a di-, tri- or tetravalent C2-C16 alkyl group and m is an integer selected from 2, 3, 4, 5 and 6. Preferably, R′ is a divalent or a trivalent C2-C16 alkyl group and m is an integer selected from 2 and 3. Most preferably the polyhydric alcohol is selected from the group consisting of ethylene glycol, 2-butyl-2-ethyl-1,3-propanediol and glycerol.

In step (i) of the claimed process, it is preferable if at least one polyhydric alcohol R′(OH)m is used, most preferably together with at least one monohydric alcohol R′OH. Thereby, the molar ratio Mg/R′(OH)m is preferably between about 1:1 and about 1:0.25, most preferably between about 1:0.8 and about 1:0.3.

The reaction conditions used in step (i) of the claimed process may vary according to the used reactants and agents. The conditions should be adjusted to give sufficiently of said magnesium compound (ab) between the magnesium compound precursor (a) and the alcohol(s) (b). According to an embodiment of the present invention, said magnesium compound precursor (a) is reacted with said at least one alcohol (b), under at least one of the following conditions:

at raised temperature, preferably at about 30 C. to about 80 C.,

for a period of about 10 min to about 90 min, preferably about 30 min,

in the presence of a C5-C10 hydrocarbon solvent, preferably heptane.

In addition to the above embodiments of step (i), other variations and reactions may also be used to produce said magnesium compound (ab), still being within the present scope of protection. Thus, with respect to step (i), the scope of protection should be interpreted under the doctrine of equivalence on the basis of what a skilled person could have done to achieve said intermediate (ab). E.g., the reaction between a tetra alkoxy silane and a dialkyl magnesium to give a magnesium dialkoxide (see Sumitomo, examples), is within the present scope of protection.

According to the invention, the product of step (i), or a similar composition, i.e. said magnesium compound (ab), is in a succeeding step (ii) reacted with a dicarboxylic acid dihalide (c) of the formula (1) to give an intermediate (abc), and said intermediate (abc) is in a third step (iii) reacted with a titanium tetrahalide TiX′4 (d) wherein X′ is a halogen.

The formula (1) of the dicarboxylic acid dihalide is:

wherein each R″ is a similar or different C1-C20 hydrocarbyl group or both R′:s form together with the two unsaturated carbons seen in the formula a C5-C20 aliphatic or aromatic ring, and X′ is a halogen.

Among non-cyclic dicarboxylic acid dihalides, the group consisting of maleic acid dihalide, fumaric acid dihalide and their R” substituted derivatives such as citraconic acid dihalide and mesaconic acid dihalide, respectively, are the most important. As the invention aims at to converting the dicarboxylic acid dihalides into their corresponding di-, oligo- or polyesters, and the di-, oligo- or polyesters as internal electron donors have to be coordinable with the magnesium dihalide and the titanium tetrahalide of the catalyst component, the cis-isomeric maleic acid dihalide and its derivatives, such as citraconic acid dihalide, are more advantageous.

However, in order to obtain a catalyst with exceptionally high activity, the R′:s of formula (1) should form together with the two unsaturated carbons of the formula a C5-C20 aliphatic or aromatic ring. Among the cyclic dicarboxylic acid dihalides, the group consisting of phthalic acid dihalide (1,2-benzene dicarboxylic acid dihalide), its hydrogenate 1,2-cyclohexane dicarboxylic acid dihalide, and their derivatives, is the most important. Most preferably, said dicarboxylic acid dihalide (c) is phthaloyl dichloride.

The amount of the dicarboxylic acid dihalide (c) may vary a lot, depending on the amount of alcohol (b) used in step (i) and the amount of alkoxide present in said magnesium compound (ab) or in said alternative intermediate (abd). It is within the present scope to adjust the amounts in order to react said intermediates with said dicarboxylic acid dihalide. According to a preferred embodiment of the present invention, in step (ii), said magnesium compound (ab) is reacted with said dicarboxylic acid halide (c) in a molar ratio Mgtotal added/(c) of between 1:1 and 1:0.1, preferably between about 1:0.6 and about 1:0.25.

The reaction conditions of step (ii) of the claimed process may vary according to the used components and their amounts. However, they should be adjusted to give sufficiently of said reaction product (abc) between said magnesium compound (ab) and said dicarboxylic acid dihalide (c). According to an embodiment of the present invention, in step (ii), said magnesium compound (ab) is reacted with said dicarboxylic acid dihalide (c), under at least one of the following conditions:

adding said dicarboxylic acid dihalide (c) under room temperature and heating the obtained reaction mixture,

keeping the reactants together at raised temperature, preferably at about 30 C. to about 80 C.,

keeping the reactants together for a period of about 10 min to about 90 min, preferably about 30 min,

reacting the reactants in the presence of a C5-C10 hydrocarbon solvent, preferably heptane.

Usually, a C5-C10 hydrocarbon solvent is used in step (ii). Then, it is preferable, that, after said magnesium compound (ab) has been reacted with said dicarboxylic acid dihalide (c), the C5-C10 hydrocarbon solvent is removed by evaporation, e.g. that heptane is used and removed at about 100 C. to about 110 C.

As was said above, it is preferable to add said reactive halogenated hydrocarbon (e) in connection with and preferably after the dicarboxylic acid dihalide (c), i.e. at the end of step (ii). Most preferably, after said C5-C10 hydrocarbon solvent, preferably said heptane, has been removed by evaporation, said intermediate (abc) is contacted with said reactive halogenated hydrocarbon (e). A convenient contacting period is about 10 min to about 90 min, preferably about 30 min.

In this reaction sequence (i)→(ii)→(iii), after said intermediate (abc) has been contacted with said reactive halogenated hydrocarbon (e), preferably in step (ii), a dissolving C5-C10 hydrocarbon, such as toluene, is preferably added. Without limiting the scope of patent protection, the hydrocarbon is believed to dissolve the reaction product and/or to lower the viscosity of its solution, thus making the intermediate (abc, including (e)) more available for reaction with the titanium tetrahalide TiX″4 (d) in the succeeding step (iii). Most preferably, a molar ratio Mgtotal added/toluene of between about 1:2 and about 1:10 is used in the addition.

In step (iii), the magnesium compound precursor/alcohol/dicarboxylic acid dihalide reaction product (abc) is reacted with at least one titanium tetrahalide TiX″4 (d), wherein X″ is a halogen. Equivalent with said titanium tetrahalide is the combination of an alkoxy titanium halide and a halogenation agent thereof, which are able to form a titanium tetrahalide in situ. However, the most preferred titanium tetrahalide (d) is titanium tetrachloride.

The amount of titanium tetrahalide (d) may vary a lot and depends e.g. on the manner of contacting it with said intermediate (abc). If the titanium tetrahalide is added to the intermediate or magnesium compound, a large stoichiometric excess thereof is not needed. Within the scope of the claimed process, the amount of titanium tetrahalide may be optimized to give a suitable catalyst. Most preferably, in step (iii), said intermediate (abc) is added into and reacted with said titanium tetrahalide (d) in a molar ratio Mgtotal added/(d) of between 1:100 and 1:1, preferably between about 1:50 and about 1:5, most preferably about 1:10.

In the reaction sequence (i)→(iii), it is preferable if in step (iii), said intermediate (abc), more preferably a solution thereof, is added slowly, most preferably dropwise, to said titanium tetrahalide (d) to form a solution of said catalyst component.

Thereby, the titanium tetrahalide is preferably hot, most preferably at 110 C. The best results are obtained, if in step (iii), a toluene solution of said intermediate (abc) is added dropwise to said titanium tetrahalide (d) at 110 C. The preferred reaction time is about 5 min to about 20 min, most preferably about 10 min.

After the reaction sequence (i)→(ii)→(iii), the reaction product, which is a precursor of, or a crude version of said catalyst component, is recovered in a recovery step (iv). Preferably, said catalyst component is recovered by continously heating a solution of said catalyst component, most preferably said toluene solution of said catalyst component, for the precipitation of the catalyst component in crude form or a precursor thereof and allowing it to settle. Immediately before said precipitation, preferably a C5-C10 hydrocarbon solvent, more preferably toluene, most preferably toluene in a molar ratio Mgtotal added/toluene of about 1:10 to about 1:100, is added to the catalyst component solution. After the crude catalyst component or the precursor has settled, the supernatant liquid is removed e.g. by decantering or siphoning.

After the recovery step (iv), said catalyst component in crude form or said precursor is optionally washed in a washing step (v). By precursor is meant a reaction product, which still is not in the form of the final catalyst component. This state of things derives from the nature of the reaction product, which may be a larger complex (see definition above) consisting of or containing one or several molecules and/or smaller complexes. Because of the loose structure of such a larger complex or complex mixture, washing will remove some of the complexes and/or molecules and essentially change the composition of the remaining solid product.

It is preferable if, in step (v), said recovered crude catalyst component or its precursor is washed with toluene, preferably with hot (e.g. 90 C.) toluene. It is also preferable, if in step (v), said recovered crude catalyst component, said recovered catalyst component precursor or said preliminary washed catalyst component is washed with heptane, most preferably with hot (e.g. 90 C.) heptane. Further, it is preferable, if in step (v), said recovered crude catalyst component, said recovered catalyst component precursor or said preliminary washed catalyst component is washed with pentane. A washing step (v) typically includes several substeps which gradually increase the magnesium dihalide content of the catalyst precursor. Such a washing sequence is, for example, one wash with toluene at 90 C., two washes with heptane at 90 C. and one wash with pentane at room temperature.

The washing can according to the invention be optimized to give a catalyst with novel and desirable properties. Thus in step (v), said recovered catalyst component is preferably washed to give the following ratio of said magnesium dihalide, said titanium tetrahalide, and said dicarboxylic acid ester as internal electron donor ED (3):

(MgX2)8-10(Tix″4)1(ED)0.7-1.3  (3)

wherein MgX2 is said magnesium dihalide, TiX″4 is said titanium tetrahalide and ED is said dicarboxylic acid ester as internal electron donor, preferably a phthalic acid di-, oligo- or polyester. X and X″ are both preferably Cl.

Finally, the washed catalyst component is usually dried, preferably by evaporation.

In appendices 1 and 2 are described the schemes of four embodiments of the present invention; two starting from a magnesium dihalide MgX2 and two starting from a dialkyl magnesium R2Mg.

In addition to the above described process, the invention also relates to an olefin polymerization catalyst component comprising a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di-, oligo- or polyester as internal electron donor ED, which has been prepared according to the above described process. By said catalyst component is meant the so called procatalyst component, i.e. the transition metal component of the whole olefin catalyst system, which system additionally includes a so called cocatalyst, i.e. an organic compound of a non-transition metal, and optionally a so called external electron donor

An advantageous embodiment of the catalyst component according to the invention comprises a magnesium dihalide, a titanium tetrahalide, and a dicarboxyl acid ester as internal electron donor ED, is essentially homogenous and has the following ratio of said magnesium dihalide, said titanium tetrahalide, and said dicarboxylic acid ester as internal electron donor ED (3):

(MgX2)8-10(TiX″4)1(ED)0.7-1.3  (3)

wherein MgX2 is said magnesium dihalide, TiX4 is said titanium tetrahalide and ED is said dicarboxylic acid ester as internal electron donor, preferably a phthalic acid di-, oligo- or polyester. Preferably X═X″═Cl. Most preferably, the catalyst component is a complex having the formula (3). This composition gives the highest activity, and when using in its preparation a polyol R′(OH)m, wherein R′ is an m-valent C1-C20 hydrocarbyl group and m is an integer selected from 2, 3, 4, 5 and 6, its morphology can conveniently be adjusted to give olefin polymers of various desired particle sizes and particle size distributions (PSD).

When adding during the preparation process of the claimed catalyst component a reactive halogenated hydrocarbon (e) of the formula (2)

R′″X′″n  (2)

wherein R′″ is an n-valent C1-C20 hydrocarbyl group, X′″ is a halogen and n is an integer selected from 1, 2, 3 and 4, the product will preferably contain more halogen than was to be expected on the basis of the MgX2 and TiX4 present. Preferably, the claimed catalyst component might contain halogen from about 10% to about 60% more than the amount of halogen calculated on the basis of the amounts of magnesium and titanium present, assuming that all of the magnesium is in the form of said MgX2 and essentially all of the titanium is in the form of said TiX4.

In the claimed catalyst component, the magnesium halide (X═Cl) structure has an X-ray diffraction pattern which differs from the X-ray diffraction pattern of pure MgCl2. It preferably shows an X-ray diffraction pattern with a lamellar thickness indicating peak at 17 2Θ, showing a clear position shift compared to normal amorphous MgCl2 which gives a height indicating peak at 15 2Θ. Indeed, according to J. Dorrepaal et al. (J. Appl.Crystallography, 1984 17, page 483), the crystal structure of MgCl2 is characterized by a=3,640 Å and C=17,673 Å. In an X-ray diffraction pattern the peak at about 15 2Θ is in the direction (003) of the c-axis, i.e. describing the height to the hexagonal unit cell, when Cu Kα radiation is used.

In addition to the above described process and catalyst component, the invention also relates to a process for the polymerization of olefins. The process is characterized by the steps of

(A) preparing a catalyst component according to the above defined process,

(B) feeding to at least one polymerization reactor said catalyst component, as well as a cocatalyst, which has the formula (4)

RpAlrX3r-p  (4)

wherein R is a C1-C10 alkyl, preferably a C1-C4 alkyl, most preferably ethyl, X is a halogen, preferably chlorine, p is an integer from 1 to (3r−1), preferably 2 or 3, most preferably 3, and r is I or 2, preferably 1, the molar ratio between said catalyst component and said cocatalyst, expressed as Al/Ti, preferably being 10-2000, more preferably 50-1000, most preferably 200-500,

optionally an external electron donor, which preferably is a silane, more preferably a C1-C12 alkyl-C1-C12 alkoxy silane, most preferably cyclohexyl methyl dimethoxy silane,

optionally a C4-C10 hydrocarbon solvent, preferably pentane, hexane and/or heptane,

preferably a chain transfer agent, which is hydrogen, and

at least one olefin monomer, which preferably is propene,

(C) carrying out the polymerization of said olefin monomer in said at least one polymerization reactor to give an olefin polymer (=homopolymer or copolymer) and

(D) recovering said olefin polymer.

In the claimed olefin polymerization process, the used (transition metal) catalyst component can be prepared according to any above described embodiment of the catalyst component preparation process.

According to one further embodiment of the invention, olefins are polymerized by the steps of

(A) providing a solid olefin polymerization catalyst component which is essentially homogenous and comprises a magnesium dihalide, a titanium tetrahalide, and a dicarboxylic acid di-, oligo- or polyester as internal electron donor ED in the following ratio (3):

(MgX2)8-10(TiX″4)1(ED)0.7-1.3  (3)

wherein MgX2 is said magnesium dihalide, TiX″4 is said titanium tetrahalide, X and/or X″ is preferably Cl, and ED is said dicarboxylic acid di-, oligo- or polyester as internal donor, preferably a phthalic acid di-, oligo- or polyester,

(B) feeding to at least one polymerization reactor said catalyst component, as well as a cocatalyst which has the formula (4)

RpAlrX3r-p  (4)

wherein R is a C1-C10 alkyl, preferably a C1-C4 alkyl, most preferably ethyl, X is a halogen, preferably chlorine, p is an integer from 1 to (3r−1), preferably 2 or 3, most preferably 3, and r is 1 or 2, preferably 1, the molar ratio between said catalyst component and said cocatalyst, expressed as Al/Ti, preferably being 10-2000, more preferably 50-1000, most preferably 200-500,

optionally an external electron donor, which preferably is a silane, more preferably a C1-C12 alkyl-C1-C12 alkoxy silane, most preferably cyclohexyl methyl dimethoxy silane,

optionally a C4-C10 hydrocarbon solvent, preferably pentane, hexane and/or heptane,

preferably a chain transfer agent, which is hydrogen, and

at least one olefin monomer, which preferably is propylene, (C) carrying out the polymerization of said olefin monomer in said polymerization reactor to give an olefin polymer (=homopolymer or copolymer) and

(D) recovering said olefin polymer.

The invention is described below by means of examples, the purprose of which merely is to illustrate the invention.

EXAMPLES BRIEF DESCRIPTION OF DRAWINGS

The following figures illustrate the examples:

FIG. 1 shows an example of a regular amorphous MgCl2 X-ray diffraction

FIG. 2 shows the IR spectrum of a catalyst.

FIG. 3 shows the activity of the PDC catalysts as a function of their Mg/Ti molar ratio.

FIG. 4 shows a simplification of the washing procedure in the examples when going from example 6 to examples 7, 8 and 9.

FIG. 5 shows the X-ray diffraction pattern of the catalyst of example 7.

FIG. 6 shows the IR spectrum of the catalyst prepared in example 6.

FIG. 7 shows the particle size distribution (PSD) of a propene polymer that was obtained when using the catalyst of example 7 in a test polymerization.

FIG. 8 shows the Ti % in some catalyst according to the invention.

FIG. 9 shows the per cent of polymer (=di, oligo or polyester), calculated as 100%—% known species, correlated to the number of —OH groups in the added alcohol.

FIG. 10 shows the proportions of TI;Mg:Donor in the catalysts.

FIG. 11 shows the activity in bulk polymerization of the catalysts in kg PP/g cat units.

FIG. 12a shows the particle size distribution (PSD) setup for the polymer obtained with the catalyst of example 9.

FIG. 12b shows the particle size distribution (PSD) setup for the polymer obtained with the catalyst of example 10.

FIG. 12c shows the particle size distribution (PSD) setup for the polymer obtained with the catalyst of example 11.

FIG. 12d shows the particle size distribution (PSD) setup for the polymer obtained with the catalyst of example 12.

FIG. 12e shows the particle size distribution (PSD) setup for the polymer obtained with the catalyst of example 13.

FIG. 13 shows an X-ray diffraction pattern of a catalyst according to the invention.

The following chemicals, chemical characterization of the catalyst components, bulk polymerisation conditions and characterization of the polymers were used in all examples.

Chemicals Used in the Examples

The magnesium alkyl (MgR2) used was BOMAG-A from Schering which was a 20% heptane solution of butyloctylmagnesium (n-C4H9)1.5(n-C8H17)0.5Mg with a magnesium content of 2.92% and a density of ζ=0.729 g/ml. Dry 2-ethyl-1-hexanol (EHA) (>99%) was used as a monohydric alcohol. 2-butyl-2-ethyl-1,3-propanediol (BEPD) was used as a first dihydric alcohol (99%). Ethylene glycol (EG) was used as a second dihydric alcohol. Glycerol (GLY) was used as a trihydric alcohol. 1,2-phthaloyldichloride (PDC) (>95%) was dried and used as chlorination agent. 1-chlorobutane (butylchloride) (BuCl) from Fluka (19750) was dried and used as a reactive halogenated hydrocarbon. Titanium tetrachloride was used as such as a titanation agent (TiCl4). Further, toluene, heptane (C7), pentane (C5), nitrogen gas (N2) and silicon oil 200/5 were used.

A 100% solution of triethylaluminium (TEA) was used as cocatalysts in the bulk polymerizations. Cyclohexyl methyl dimethoxy silane (CMDS) was used as external donor in the polymerizations.

Chemical Characterization of the Catalyst Components

The catalyst components were characterized with respect to their chemical composition by measuring their Mg, Ti and Cl content. The Mg and Ti analysis was started by dissolving the samples in a mixture of nitric and hydrofluoric acid. The metal was measured by flame atomic absorption with a nitrous oxide/acetylene flame. Chloride was determined after dissolution in diluted sulphuric acid by potentiometric titration with a standard silver nitrate solution.

The determination of the phthalic esters (diethylphthalate DEP and dioctylphtalate DOP) and the phthalic anhydride (PA) were done by first dissolving the sample in acetone. The samples were filtered and run by solution chromatography (HPLC). Each component was identified by comparing the respective retention time and ultra violet (UV) spectra with standard components.

To check the conversion rate of the ethanol (EtOH), 2-ethyl-hexanol (EHA), or other alcohol added in the synthesis, the alcohol content of the catalysts were measured by gas chromatography (GC). A Hewlett Packard 5890 GC with a 60 m DB-1 column was used for the GC analyses. The column had an diameter of 0.25 mm with a film thickness of 1 μm. An FID detector was used.

The WAXS X-ray diffraction patterns were collected in reflection mode between 2and 70 2Θ with a Siemens D500 instrument. The CuKα radiation wavelength was 1.54 Å.

The IR spectra were taken by a Nicolet 510 FTIR equipment with 2 cm−1 resolution.

Bulk Polymerization of Propene

Propene was polymerized in a stirred tank reactor having a volume of 5 1. TEA as a cocatalyst, CMDS as an external donor and 300 ml of n-pentane were mixed and allowed to react for 5 minutes. Half of the mixture was added to the polymerization reactor and the other half was mixed with said catalyst component. After additional 5 minutes the catalyst/TEA/CMDS/n-pentane mixture was introduced into the reactor. The Al/Ti mole ratio was 250 and the Al/CMDS mol ratio was 10 mol/mol. 70 mmol hydrogen and 1400 g of propene were introduced into the reactor and the temperature was raised within 15-30 minutes to 70 C. The polymerization time was 60 minutes.

Characterization of the Polymers

The polymers were characterized with respect to their melt flow rate (MFR2), bulk density (BD) and the fraction of total solubles in xylene (XS). MFR (g/10 min) was measured using the standard ISO 1133 (2.16 kg load, 230 C.). The bulk density (in kg/m3) of the material was measured from a 100 ml cylinder. The amount of total xylene solubles (in wt-%) was measured by dissolving a polymer sample in 250 ml of boiling xylene, precipitating the isotactic material at 25 C. and evaporating the solvent from the soluble sample fraction.

Examples 1 to 4

The setup of the examples is listed in Table 1.

TABLE 1
The experimental setup for examples 1-4
Example MgR2/ROH Diol BuCl Mg/Ti Mg/PDC
1 1:2 No No 1:10 1:1
2 1:2 Yes Yes 1:10 1:0, 5
3 1:3 No Yes 1:2 1:0, 5
4 1:3 Yes Yes 1:10 1:0, 5

In comparative example 1, no butyl chloride was used. In the comparative example 1 and example 3, no diol was used. The synthesis was started by introducing 35 mmol of MgR2 (BOMAG-A) into a 100 ml glass reactor at room temperature. The molar ratio MgR2/C7 in this solution was 1:7.

In the next step EHA was added in a molar ratio MgR2/EHA of 1:2 or 1:3 depending on the experimental setup. After the addition of EHA, the temperature was increased to 60 C. and the reactants were allowed to react with each other for 30 min. After this the reaction solution was cooled down to room temperature. Depending of the experimental setup, the second alcohol, i.e. BEPD was introduced into the reactor.

The MgR2/BEPD molar ratio was 1:0.5. Again, the temperature was increased to 60 C. and the reactants were allowed to react with each other at this temperature for 30 min after which the temperature was lowered to room temperature.

The next reagent to be added was the ortho-phthaloyl dichloride (PDC). This chlorination agent was added in a Mg/PDC molar ratio of 1:1 or 1:0.5 according to Table 1. The temperature was increased to 60 C. and the reaction solution was kept at this temperature for 30 min. After this the temperature of the reaction solution was lowered to room temperature. Depending on the experimental setup the second chlorination agent, butylchloride (BuCl) was now added at a Mg/BuCl molar ratio of 1:1. Again the temperature was increased to 60 C. and the reaction solution was kept at this temperature for 30 min.

In examples 2 and 3 silicon oil was added as particle size modifier. It was introduced directly onto the hot solution. The molar ratio of the added silicon oil to magnesium was 5:1, calculated as mol silice per mol magnesium (Si/Mg).

A portion of toluene was added either to the hot Mg solution (examples 1 and 4) or to the receiving TiCl4 solution (examples 2 and 3) to increase the solubility of the components. The C6H5CH3/Mg molar ratio was 5:1.

While the Mg-solution was being prepared, a portion of TiCl4 was introduced into a 250 ml thermostated glass reactor. The TiCl4/Mg molar ratio was 2:1 or 10:1.

A portion of TiCl3OEt was added to the TiCl4 solution in examples 1, 2 and 3. The TiCl3OEt/Mg molar ratio was 3:1. The temperature of this receiving solution was increased to 110 C.

The Mg-solution was then added dropwise to this hot TiCl4 solution. The whole addition took 20 min. After this the reactants were allowed to react with each other for 5 min (examples 2 and 4) or 1 h (examples 1 and 3).

After the components had reacted with each other, the reaction solution was allowed to cool down to 90 C., after which 40 mol heptane (C7) was added to precipitate the catalyst complex. After this the supernatant liquid was siphoned off.

The catalyst component was washed with toluene or a mixture of toluene and TiCl4. The toluene wash was carried out at 90 C. for 20 min, under stirring. Then the catalyst component was washed two times at 90 C. for 10 min with heptane. The C7/Mg molar ratio in these washes was 40:1. Thereafter, the catalyst component was washed with pentane (C5) for 10 min at room temperature. The C5/Mg molar ratio was 50:1. Finally, the catalyst component was dried under a stream of nitrogen. All the catalyst were characterized chemically according to the description above and they were test polymerized as described above. All the results are listed in Table 2, in which EtOH stands for ethanol.

TABLE 2
Comparative
Catalyst example 1 Example 2 Example 3 Example 4
Mg (wt-%) 8.0 14.1 16.4 11.9
Mg (mol/100 g 0.33 0.58 0.68 0.49
catalyst)
Ti (wt-%) 5.8 1.8 2.5 3.1
Ti (mol/100 g catalyst) 0.12 0.04 0.05 0.07
BEPD (wt-%) 0.27 0.48
BEPD (mol/100 g 0.002 0.003
catalyst)
EHA (wt-%) 0.21 0.001 0.13
EHA (mol/100 g 0.002 0.001 0.001
catalyst)
EtOH (wt-%) 0.76 0.27
DEP (wt-%) 8.54 1.42 1.27
DEP (mol/100 g 0.038 0.006 0.006
catalyst)
DOP (wt-%) 28.4 16.8 11.1 33.6
DOP (mol/100 g 0.073 0.043 0.028 0.086
catalyst)
PA (wt-%) 1.46 0.09 0.9
Mg (molar ratio) 2.7 15.4 12.9 7.6
Ti (molar ratio) 1 1 1 1
Donor (molar ratio) 0.9 1.3 0.7 1.3
Toluene (wt-%) 0.71 0.22 0.07
C5 (wt-%) 1.02 0.46 0.37
C7 (wt-%) 2.15 1.18 0.70
Activ. (kg PP/g cat) 4.8 7.00 10.6 26.6
Activ. (kg PP/g Ti) 83 389 424 858
BD (kg/m3) 400 350 450 430
MFR2 (g/10 min) 10.3 8.3 10.4 6.2
XS (wt-%) 2.4 1.7 1.6

The results of the catalyst synthesis show that:

1. BuCl greatly effects the Mg/Ti molar ratio.

2. There is an oligo- or polyester formation if a diol and a phthaloyl dichloride is used in the synthesis of the donor compound.

3. The presence of DOP in the precipitating (MgCl2)xTiCl4DOP complex favours the outcome of regular amorphous crystal structure of the complex MgCl2.

4. Ethers are present in the (MgCl2)xTiCl4DOP catalyst complex.

5. BuCi greatly improves the catalyst activity.

6. Optimum composition of the catalyst complex is (MgCl2)xTiCl4DOP, wherein X is from about 7 to about 10.

7. Activities of up to 27 kg PP/g cat are reached.

Most of the catalysts originating from a synthesis where PDC had been used showed a quite regular amorphous MgC2 X-ray diffraction pattern. As an example of these patterns, the pattern of example 2 is shown in FIG. 1. The 2Θ-value is given in abscisse. Only one of the catalysts belonging to this latter group showed a strongly disturbed X-ray pattern, while the rest of the followed nicely the above mentioned features. However one pattern (in FIG. 13) showed an unusual halo between 18 and 22 2Θ reflecting the haloformation significant for MgCl2(Mg(OR)2)2 complexes.

In all the IR spectra from the catalysts prepared out of PDC there were clear peaks indicating the presence of ether at 1080 cm−1. In all these spectra there were also clear peaks at 1860 and 1760 cm−1 indicating the presence of an acid anhydride. An example of these spectra is shown in FIG. 2 where the IR spectrun of the catalyst component of example 4 is shown. The wavenumber is shown in abscisse and the % of transmittance in ordinate. (1) peak indicates ether and (2) peak indicates acid anhydride.

It is believed that BuCl reduces the TiCl4 content relative to the MgCl2 content of the catalyst component. This can be seen in FIG. 3 where the activities (in orelinate) of the PDC catalysts are shown as a function of their Mg/Ti molar ratio (in abscisse). Here it can be seen that the three catalysts that has been chlorinated by BuCl are forming an own group in the right upper corner of the figure, while the catalysts that have not been contacted with BuCl are forming a group in the lower left corner of the figure. The graph indicates that there is an optimum activity corresponding to an Mg/Ti molar ratio of 7-10. This finding is supported by an another result from examples 2-4 indicating that a moderate washing of the catalyst is optimum.

Examples 5 to 8

The experimental setups for examples 5-8 are listed in Tables 3-6. The chemicals used were identical to those used in examples 1-4, as well as the characterisation methods. The catalysts were polymerized according to the polymerization process described above.

In example 5 the amount of BuCl is increased to the double compared to example 4. Example 6 was identical to example 5, but no heptane was added to the TiCl4 solution. The principle of the catalyst washing in example 6 is shown in FIG. 4 left column.

Example 7 was identical to example 6, but a larger part of the monoalcohol was replaced by the diol. Example 8 was a repetition of the third (example 7) with the exception that the mono and dihydric alcohols were mixed together and added to the catalyst synthesis in a joined addition step. The principle of the catalyst washing is in examples 7-9 is shown in FIG. 4, right column.

Preparation of the Catalyst Components

In the following, example 6 is described. The other examples were performed in a similar way. Into a 250 ml glass reactor was introduced 40 ml of a 20% heptane solution of BOMAG-A (35.01 mmol). Onto this was added 11.0 ml (70.01 mmol) of EHA. The temperature of the reaction solution was increased to 60 C. and the reactants were allowed to react with each other for 30 min. Then, 2.805 g (17.50 mmol) of BEPD was first heated with 2 ml of heptane in a septum bottle to 40 C. to obtain a feed solution. This solution was siphoned to the main reactor. To secure complete transfer, the septum bottle was rinsed with another portion of 1.5 ml of heptane that was also siphoned to the main reactor. Again the reactants were allowed to react for 30 min. 2.52 ml (3.554 g, 17.50 mmol) of PDC was introduced and allowed to react for 30 min. The last reagent when preparing the Mg complex solution was 4.000 ml (76.570 mmol) of BuCl that also was allowed to react for 30 min. 20 ml (187.8 rnmol) of toluene was added as last step in the preparation of the Mg complex solution in order to decrease its viscosity.

The following step in the catalyst synthesis was the addition of the Mg complex into 38.48 ml (350.1 mmol) of TiCl4. The addition was done dropwise, the TiCl4 solution having a temperature of 110 C. The catalyst was allowed to be formed in this solution for 5 min after which the TiCl4 solution was allowed to cool down to 90 C. after which 110 ml of heptane was added (in examples 5 and 6) to improve the precipitation of the catalyst. The reaction solution was kept at 90 C. for 20 min after which the catalyst was allowed to settle and the liquid was siphoned off. After this, the catalyst was washed twice with a 130 ml portion of a 10% TiCl4 toluene solution at 90 C. for 30 min. Finally the catalyst was washed twice with 180 ml portions of heptane also at 90 C. for 30 min and lastly with a 150 ml portion of pentane at room temperature for 15 min. The catalyst was dried from hydrocarbons under a stream of nitrogen.

In Tables 3-6, mol.ratio stands for molar ratio, stirr. stands for stirring time in minutes, settl. stands for settling time in minutes and 22→60 means that the temperature was risen from 20 to 60 C. No stirring was used during the drying.

TABLE 3
Example 5 mol. ratio mmol ml C.
BOMAG-A  (20%/C7) 1 35.01 40.0
EHA 2 70.01 11.0
BEPD 0.5 17.50
PDC 0.5 17.50 2.5
BuCl 2.2 76.57 8.0
Toluene 20.0
TiCl4 (110 C.) 10 350.1 38.5
Precipitation in C7 20 5 90
stirr. settl.
Washings: (min) (min) ml C.
Toluene (+10% TiCl4) 30 5 90
C7 26 2 90
C7 28 2 90
C5 19 2 90
Drying (N2) 46 min 22→60

TABLE 4
Example 6 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.0
EHA 2 70.01 11.0
BEPD 0.5 17.50
PDC 0.5 17.50 2.5
BuCl 2.2 76.57 8.0
Toluene 20.0
TiCl4 (110 C.) 10 350.1 38.5
stirr. settl.
Washings: (min) (min) ml C.
Toluene (+10% TiCl4) 30 4 90
C7 36 3 90
C7 32 6 90
C5 30 2 90
Drying (N2) 45 min 22→60

TABLE 5
Example 7 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.0
EHA 1.5 52.51 8.3
BEPD 0.75 26.25
PDC 0,4 14,00 2,0
BuCl 2,2 76,57 8,0
Toluene 20,0 
TiCl4 (110 C.) 10 350,1  38,5 
stirr. settl.
Washings: (min) (min) ml C.
Toluene (+10% TiCl4) 36 5 130 90
C7 30 3 150 90
C7 30 3 145 90
C5 30 3 150 90
Drying (N2) 45 min 22→60

TABLE 6
Example 8 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.0
EHA 1.5 52.51 8.3
BEPD 0.75 26.25
PDC 0,4 14,00 2,0
BuCl 2,2 76,57 8,0
Toluene 20,0 
TiCl4 (110 C.) 10 350,1  38,48
stirr. settl.
Washings: (min) (min) ml C.
Toluene (+10% TiCl4) 44 140 90
C7 25 27 150 90
C7 30 7 150 90
C5 30 9 155 90
Drying (N2) 37 min 22→60

The catalysts and the polymers obtained were analyzed and characterized as described above for examples 1-4. The results are listed in Table 7.

TABLE 7
Catalyst Example 4b Example 5 Example 6 Example 7 Example 8
Mg (wt-%) 11.5 8.8 13.4 13.4 12.6
Mg (mol/100 g catalyst) 0.473 0.362 0.551 0.551 0.519
Ti (wt-%) 2.9 4.5 2.1 3.2 2.4
Ti (mol/100 g catalyst) 0.061 0.094 0.044 0.067 0.050
BEPD (wt-%) 0.01 0.96 0.65 1.66 1.24
BEPD (mol/100 g catalyst) 0.000 0.006 0.004 0.010 0.008
EHA (wt-%) 0.24 0.45 0.44 0.33 0.33
EHA (mol/100 g catalyst) 0.0018 0.0035 0.0034 0.0025 0.0025
DOP (wt-%) 35.5 41.8 34.7 21.9 21.1
DOP (mol/100 g catalyst) 0.091 0.107 0.089 0.056 0.054
PA (wt-%) 1.0 0.8 1.7 1.2 1.0
Mg (mol Mg/mol Ti) 7.8 3.9 12.6 8.3 10.3
Donor (mol Donor/mol Ti) 1.5 1.1 2.0 0.8 1.1
Toluene (wt-%) 0.09 0.17 0.04 0.32 0.37
C5 (wt-%) 0.6 0.17 0.06 0.39 0.45
C7 (wt-%) 0.15 0.40 0.15 1.90 8.73
Volatil. tot. (wt-%) 0.84 0.74 0.25 2.61 9.55
Activ. (kg PP/g cat) 19.4 1S.2 12.0 21.2 19.1
Activ. (kg PP/g Ti) 669 339 569 472 795
BD (kg/m3) 470 400 290 310 300
MFR2 (g/10 min) 6.5 7.2 10.5 8.0 8.9
XS (wt-%) 3.2 2.3 3.1

The examples 5 to 8 show that very good morphology of the polymer material can be achieved if the heptane precipitation of the catalyst is left out from the catalyst synthesis. 65% of the polymer particles had a particle size between 0.5 and 1.0 mm. The catalyst yield in the catalyst synthesis was the same even if heptane precipitation was not used.

Increased amount of oligo or polyester ingredients added to the catalyst synthesis increased the amount of organic material in the catalyst from 2 to 10%.

X-ray diffraction patterns were taken from all catalysts. The characteristic features are a quite sharp peak at 50 2Θ describing the broadness of the crystal plates and, a halo formation between 30 and 35 2Θ describing the intermediate reflecting layers. There was however, a clear difference. In crystalline MgCl2 there is an intensive peak at 15 2Θ indicating the lamellar thickness. The position of this peak is the same also for amorphous MgCl2 even if it is much lower. The results showed that there had been a clear shift of the lamellar thickness indicating peak in all the X-ray diffraction patterns coming from the catalysts in this test series. In Table 8 the position of the lamellar thickness indicating peak for the catalysts in this test series is listed. In all cases the peak had shifted upwards to the region of about 17 2Θ. These results indicate that there is forming a new type of more tightly packed MgCl2 crystals in the lamellar thickness direction in the material formed in the type of stoichiometric preparation route described here (see FIG. 5).

The IR spectrum of the catalyst prepared in example 6 is shown in FIG. 6, and the PSD of the polymer from example 7 is shown in FIG. 7, where sieve size (mm) is given in abscisse and % of polymer in ordinate.

TABLE 8
The position of the lamellar thickness indicating peak in the X-ray
diffraction pattern for crystalline MgCl2, amorphous MgCl2 and
for the catalysts of examples 5 to 8.
Position of the lamellar thickness
Material indicating peak
Crystalline MgCl2 15.0 2θ
Amorphous MgCl2 15.0 2θ
Example 5 17.1 2θ
Example 6 17.0 2θ
Example 7 16.5 2θ
Example 8 16.1 2θ

FIG. 6 shows the IR spectrum for the catalyst of example 6989.

The polymerization results are listed in Table 9 together with a description of the polymer morphology.

TABLE 9
The polymers and their bulk density
Bulk density
Example (kg/m3)
4b 470
6 290
7 310
8 300

The first polymer (example 4b) showed a broad particle size distribution (PSD). The highest BD (470 kg/m3) was seen in this material. The morphology improved greatly when the heptane addition was left out in the precipitation step. The improvement was seen already when preparing the catalyst, as a catalyst precipitate that had much better settling properties was achieved. The same improvement was then seen in the morphology of the polymer that was produced when using this catalyst in the test polymerization. Over 65% of the material of example 6 has a particle size that is between 0.5 mm and 1.0 mm. The amount of fines (defined as particles below 0.1 mm) is below 1%. The amount of particles having a particle size of over 2 mm is also low, i.e. around 1%.

Examples 9 to 13

The experimental setups for examples 9-13 are listed in Tables 10-14 and the results are listed in Table 15.

Preparation of the Catalysts

40.0 ml (35.01 mmol) of MgR2 was added into a glass reactor. 11.0 ml (70.01 mmol) of EHA was added into the reactor and allowed to react with the MgR2. The reactants were allowed to react with each other for 30 min. After this, 17.50 mmol of the second alcohol component was added according to the description. To ensure full equilibrium, the reactants were allowed to react with each other for 30 min. 2.52 (17.50 mmol) of PDC was added and allowed to react for 30 min. The last component to be added in the Mg complex was BuCl, 4.00 ml (38.28 mmol) of this substance was added and allowed to react for 20 min. All reaction steps were carried out at a temperature of 60 C. Last, the heptane of the MgR2 solution was evaporated away at 107 C. and replaced with 10 ml (94 mmol) of toluene. The formed Mg complex was now added dropwise to 38.48 ml (350.1 mmol) of TiCl4 at 110 C. The components were allowed to react for 5 min after which 100 ml (938 mmol) of toluene was added. The components were allowed to react for 30 min after which mixing was stopped and the catalyst was allowed to settle. Both the settling time and the precipitate volume were recorded. After siphoning off the reaction solution, the catalyst was washed first with a 10 V-% TiCl4 solution of toluene, twice with heptane and last with pentane. The washings were carried out as stated in Table 10. Finally the catalysts were dried under a stream of nitrogen.

TABLE 10
Example 9 mol. ratio mmol
BOMAG-A  (20%/C7) 1 35.01 40.00 ml
EHA 2 70.01 11.00 ml
BEPD 0.5 17.50 2.81 g
PDC 0.5 17.50 2.52 ml
BuCl 1.1  38.285 4.00 ml
EVAPORATION condense 30.33 g
Toluene 5 ml
TiCl4 (110 C.) 10 350.1  38.48 ml
stirr. settl.
Washings: (min) (min) ml C.
Settling 0 15 90 . . . 70
Toluene 30 30 130 90
Toluene (+10% TiCl4) 45 970 120 90
C7 35 10 180 90
C7 28 15 170 90
C5 20 1063 150 22
Drying (N2) 75 min 22→60

TABLE 11
Example 10 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.00
EHA 2 70.01 11.00
EG 0.5 17.50 0.98
PDC 0.5 17.50 2.52
BuCl 1.1 38.28 4.00
EVAPORATION
Toluene 5.0
TiCl4 (110 C.) 10 350.1 38.48
stirr. settl.
Washings: (min) (min) ml C.
Toluene 35 10 200 90
Toluene (+10% TiCl4) 30 5 185 90
C7 16 4 170 90
C7 22 4 180 90
C5 25 5 210 22
Drying (N2) 15 min 22→60

TABLE 12
Example 11 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.00
EHA 2 70.01 11.00
EG 0.5 17.50 0.98
PDC 0.5 17.50 2.52
BOMAG-A  (20%/C7) 0.4 14.00 16.0
BuCl 1.1 38.28 4.00
EVAPORATION condense
Toluene 15
TiCl4 (110 C.) 10 350.1 38.48
Cooling
stirr. settl.
Washings: (min) (min) ml C.
Toluene 30 15 120 90
Toluene (+10% TiCl4) 31 6 135 90
C7 05 970 150 90
C7 25 8 205 90
C5 18 4 210 22
Drying (N2) 37 min 22→60

TABLE 13
Example 12 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.00
EHA 2 70.01 11.00
Glycerol 0.5 17.50 1.29
PDC 0.5 17.50 2.52
BuCl 1.1 38.29 4.00
EVAPORATION condense
Toluene 15.0
TiCl4 (110 C.) 10 350.1 38.48
stirr. settl.
Washings: (min) (min) ml C.
Toluene 28 12 120 107
Toluene (+10% TiCl4) 20 21 140 90
C7 26 11 150 90
C7 24 22 165 90
C5 15 9 170 22
Drying (N2) 36 min 22→60

TABLE 14
Example 13 mol. ratio mmol ml
BOMAG-A  (20%/C7) 1 35.01 40.00
EHA 2.5 87.52 13.75
EtOH 0.1 3.50 0.20
EG 0.05 1.75 0.10
PDC 0.5 17.50 2.52
BOMAG-A  (20%/C7) 0.2 7.00 8.00
i-PDC 0.05 1.75 0.36
BuCl 1.1 38.28 4.00
EVAPORATION
Toluene 10
TiCl4 (110 C.) 10 350.06 38.48
Cooling
stirr. settl.
Washings: (min) (min) ml C.
Toluene 27 25 80 90
Toluene (+10% TiCl4) 23 20 140 90
C7 25 14 150 90
C7 30 968 190 90
C5 27 22 175 22
Drying (N2) 40 min 22→60

TABLE 15
Catalyst Example 9 Example 10 Example 11 Example 12 Example 13
Mg (wt-%) 16.3 14.1 14.1 13.7 13.9
Mg (mol/100 g catalyst) 0.671 0.580 0.580 0.564 0.572
Ti (wt-%) 3.3 3.0 7.1 3.3 2.7
Ti (mol/100 g catalyst) 0.069 0.063 0.148 0.069 0.056
BEPD (wt-%) 2.2
BEPD (mol/100 g catalyst) 0.014
EHA (wt-%) 0.3 0.35 2.8 2.8 1.1
EHA (mol/100 g catalyst) 0.0023 0.0027 0.0215 0.0215 0.0084
DOP (wt-%) 27.7 17.6 18.4 23.2 21.8
DOP (mol/100 g catalyst) 0.071 0.045 0.047 0.059 0.056
Mg (mol Mg/mol Ti) 9.7 9.3 3.9 8.2 10.1
Donor (mol Donor/mol Ti) 1.0 0.7 0.3 0.9 1.0
Diol BEPD EG EG Glycerol EG+EtOH
Activ. (kg PP/g cat) 26.0 33.8 13.1 21.2 20.0
Activ. (kg PP/g Ti) 788 1127 184 642 743
BB (kg/m3) 330 380 410 310 380
MFR2 (g/10 min) 8.8 6.7 7.5 7.9 11.4
XS (wt-%) 4.1 2.75

The resulting yields in the catalyst synthesis were in general high.

The amounts of Ti in these catalysts are also shown in FIG. 8.

No additional amount of DEP could be found in the catalyst of example 13. This example was the only one where DEP could be expected to be found because some ethanol had been added.

The % of polymer (=di-, oligo- or polyester), calculated as 100 %—% known species are correlated to the number of —OH groups in the added alcohol in FIG. 9, where (1) refers to EHA, (2) to ethylene glycol and (3) to glycerol.

The molar ratios between Mg, Ti and the donor are shown in FIG. 10, where Ti is presented in the first column, Mg in the second column and donor in the third column. The Figure shows that the catalysts can be divided into two groups, one group where the Mg:Ti:Donor ratio is close to 9:1:1 and a second group where less Mg is present.

The activities of the catalysts are shown in FIG. 11 in kg PP/g.cat. The catalysts can be divided into two groups depending on their activity, one group showing a high activity of above 20 kg PP/g cat and a second group showing lower activity.

The particle size distribution (PSD) of the polymer sample was measured using a Fritsch Pulverisette equipment with a sieving set consisting of 5, 4, 2, 1, 0.5, 0.18, 0.1, 0.056, 0.036 mm sieves and <0.036 mm (pan).

FIGS. 12a-12 e shows the PSD (particle size distribution) diagrams for the five polymers achieved with the catalysts in this test series. The results showed that the catalysts of examples 10, 11 and 12, showed a clearly narrower PSD compared to the catalysts of examples 9 and 13.

A more narrow particle size distribution (PSD) can be produced with ethylene glycol. The main particle size (PS) is then 1 mm.

Very good activities can be reached when using ethylene glycol in the catalyst synthesis. Activities of almost 34 kg PP/g cat were achieved.

Examples 14 to 17

All the chemicals used were identical to the chemicals used in previous examples. The only chemical not defined earlier but used in this study was 1,4-dichlorobutane (DCB) that was used as a reactive halogenated hydrocarbon.

Preparation of the Catalysts

The preparation of the catalysts was started by adding 40.0 ml (35.01 mmol) of MgR2 (BOMAG-A) to a 250 ml glass reactor. To this a mixture of both the mono alcohol and the diol, i.e. 11.0 ml (70.01 mmol) of EHA and 17.50 mmol of either BEPD or EG was added. The temperature of the reaction solution- was increased to 60 C. and the reaction components were allowed to react with each other for 30 min. After this 2.52 ml (17.50 mmol) of PDC was added at 25 C. Again, the temperature was raised to 60 C. and the components allowed to react for 30 min. The heptane was now evaporated from the reaction solution at a temperature of 105 C., this to improve the reaction possibilities for the chlorinated hydrocarbons. After the evaporation of the heptane 45.67 mmol (5.0 ml) of either BuCl or DCB was added. The molar ratio between Mg and the chlorination agent was thus about 1:1.3 in both cases. After a 30 min reaction time 20.0 ml (188 mmol) of toluene was added. This Mg complex solution was then added dropwise to 38.48 ml (350.1 mmol) of TiCl4 at 110 C. The components were allowed to react with each other for 10 min after which the solution was cooled down to 105 C. and 150 ml of toluene was added. After this the formed precipitate was allowed to settle. The settling time and the precipitate volume were recorded. When the settling step was complete the clear solution was siphoned off and the precipitate washed first once with 150 ml of toluene at 90 C. for 30 min, then twice with 150 ml of heptane at 90 C. for 30 min and last with 150 ml of pentane at room temperature for 20 min. Last, the catalyst was dried under a stream of nitrogen. The experimental setup, i.e. when BEPD or EG or when ButCl or DCB have been used in this test series, are listed in Table 16.

TABLE 16
The experimental setup of examples 14 to 17
Example Diol used Chlorinated hydrocarbon used
14 BEPD DCB
15 EG DCB
16 BEPD BuCl
17 EG BuCl

The yield of the catalyst mass from the catalyst synthesis was calculated on the basis of how much Mg was fed into the synthesis in the form of MgR2 (0.8507 g) and by comparing this amount with the amount of Mg found in the resulting catalyst. The results are listed in Table 17. In Tables 18, 19 and 20 are listed the results of the catalyst analyzes: Mg, Ti and DOP %, molar ratios Mg:Ti:DOP and calculated and measured Cl contents, respectively.

TABLE 17
The yield percent of the catalysts of examples 14 to 17
Example Yield of catalyst (g) Calculated yield1
14 6.0 91
15 3.4 69
16 5.7 99
17 6.8 98
1Calculations based on: Yield % = (Catalyst yield (g) * Mg %)/0.8507 (g)

TABLE 18
The Mg, Ti and DOP in the catalysts of examples 14 to 17
Example 14 15 16 17
Mg (wt-%) 12.9 17.3 14.9 12.2
Mg (mol/100 g catalyst) 0.53 0.71 0.61 0.50
Ti (wt-%) 3.6 3.7 2.2 4.1
Ti (mol/100 g catalyst) 0.08 0.08 0.05 0.09
DOP (wt-%) 30.9 22.4 27.9 29.8
DOP (mol/100 g catalyst) 0.08 0.06 0.07 0.08

TABLE 19
The molar ratios between Mg:Ti:DOP in the catalysts of examples
14 to 17
Examples 14 15 16 17
Mg 7.1 9.2 13.4 5.9
Ti 1 1 1 1
DOP 1.05 0.74 1.56 0.89

TABLE 20
The calculated amount of Cl compared to the measured
amounts of Cl in examples 14 to 17
Example 14 15 16 17
Cl (wt-%), calculated 37.7 50.5 43.5 35.6
Cl (wt-%), measured 47.1 50.5 52.5 48.8

The polymerization results are listed in Table 21 together with figures about the MFR and BD of the polymers.

TABLE 21
Test polymerization results from bulk test polymerization of
examples 14 to 17
Example 14 15 16 17
Activity (kg PP/g cat.) 24.1 28.0 21.8 23.0
Activity (kg PP/g Ti) 669 758 989 562
MFR 2.16 kg (g/10 min) 6.3 8.3 8.4 7.4
BD (kg/m3) 290 310 300 410

The polymerization results showed that if the BEPD diol is exchanged to EG, this has a positive effect on the activity of the catalyst. In the case BuCl was used as chlorinated hydrocarbon there was an activity increase from 21.8 to 23.0 kg PP/g cat., and if the DCB had been used as the chlorinated hydrocarbon there was an activity increase from 21.8 to 28.0 kg PP/g cat., thus showing a 28% activity increase in the best case.

The polymerization results also showed that when using the DCB as chlorinated hydrocarbon a higher activity was achieved compared to when using BuCl. This was the case both when using BEPD and when using EG as diol. In the former case the activity increased from 21.8 to 24.1 kg PP/g cat, and in the later case the activity increased from 23.0 to 28.0 kg PP/g cat, i.e. a 22% increase in activity.

In Table 22 the Mg/Ti molar ratio in the catalysts is compared to the activities of the catalysts. According to the results there is a steady growth in activity the higher the Mg/Ti molar ratio. Here an increase in activity from 23.0 kg PP/g cat for the ratio of 5.9 to 28.0 kg PP/g cat for the Mg/Ti ratio of 9.2 is seen.

TABLE 22
The molar ratios between Mg:Ti in the catalysts and their activities
Example 14 15 16 17
Mg/Ti 7.1 9.2 13.4 5.9
Activity (kg PP/g cat.) 24.1 28.0 21.8 23.0
Activity (kg PP/g Ti) 669 758 989 562

In Table 23 the DOP/Ti molar ratio is listed together with the activity values for the catalysts. The results showed that the lower the DOP/Ti ratio the higher the activity.

In Table 23 an increase in activity from 21.8 kg PP/g cat to 28.0 kg PP/g cat is seen when the molar ratio of DOP/Ti decreases from 1.6 to 0.7.

TABLE 23
Correlation between the DOP/Ti ratio and the activity
of the catalysts
Example DOP/Ti (mol/mol) Activity (kg PP/g cat)
14 0.7 24.1
15 0.9 28.0
16 1.0 21.8
17 1.6 23.0

In Table 24 the particle size fractions in the test polymers are listed.

TABLE 24
The PS fractions in the test polymers of examples 14 to 17, in % of
polymer on sieve
Example
Sieve size/mm 14 15 16 17
  5.0 9.5 5.7 1.3 2.3
  4.0 2.1 1.7 0.2 3.5
  2.0 4.6 9.3 1.8 26.0
  1.0 4.6 16.4 2.3 27.3
  0.5 6.8 16.2 11.0 16.2
  0.18 45.8 25.2 76.4 18.6
  0.10 19.0 19.1 6.2 5.0
  0.056 7.0 6.4 0.8 1.0
  0.036 0.6 0.2 0.1 0.1
<0.036 0.0 0.0 0.0 0.0

The results showed a drastic difference in the PSD depending on which diol had been used. If BEPD had been used the main PS fraction was on the 0.18 mm sieve, if EG had been used the main PS fraction was on the 1 to 0.18 mm sieve. This effect was even more pronounced when BuCl had been used as chlorination agent compared to DCB. The results also showed that if BEPD had been used, the PSD was very sharp, up to 75% of the particles could be found on one sieve, the 0.18 mm sieve. Again if EG had been used the PSD was much broader and only about 25% of the material could be found on the main sieve, i.e. the 1 mm sieve. This can clearly be seen in Table 25 where the per cent material representing the biggest fractions in the polymer PSD are listed (i.e. the fractions on the 0.18 mm and the 1 mm sieves).

TABLE 25
The percent of the polymer material in the two main
fractions of the PSD
Example % at 0.18 mm sieve % at 1 min sieve
14 45.8 4.6
15 25.2 16.4
16 76.4 2.3
17 18.6 27.3

For comparison a catalyst was prepared in the absence of diol. When this kind of catalyst is used in polymerization the polymer particles tend to form agglomerates giving a broad PSD of the resulting polymer material. This is shown in a polymer PSD that has been produced with said catalyst. When replacing a part of the monoalcohol (EHA) used in this recipe with a diol a much narrower PSD can be achieved. The recipe is presented in Table 26 and the results of the sieve operation is presented in Table 27.

TABLE 26
Comparative example mole ratio mmol ml
BOMAG-A  (20%/C7) 1 26.55 30.0
EHA 2 53.10 8.3
PDC 1 26.55 3.8
TiCl4 (95 C) 10 265.5 29.2
Toluene 80+60
Washings: Time (min) ml C.
Toluene 50 148 90
Toluene 15 56 22→85
C7 32 68 22→85
C7 32 50 <35
C5 15 60 22
Drying (N2) 42 min 22→55

TABLE 27
Sieve size/mm wt-%
  5.0 11
  4.0 3
  2.0 9
  1.0 14
  0.5 22
  0.18 30
  0.10 8
  0.056 2
  0.036 0
<0.036 0

The bulk density values (BD) for the polymers listed in Table 21 showed that there was a strong correlation between the bulk density and the diol used in the synthesis. If EG had been used the BD was higher. This shows up as a BD increase from 290 to 310 when going from example 14 to example 17, i.e. from BEPD to EG and as a BD increase from 300 to 410 when going from example 16 to example 17, i.e. from BEPD to EG.

Conclusions

1. (1,4)-butyl-dichloride gives up to 20% higher activity to the catalyst compared to BuCl

2. EG gives 30% higher catalyst activity compared to BEPD

3. EG gives a coarse and a fine catalyst precipitate fraction, BEPD gives only a fine

4. EG gives faster settling time for the catalyst precipitate, BEPD gives slower settling time

5. EG gives smaller catalyst precipitate volume than BEPD

6. EG gives main PS of PP at 1 mm, BEPD at 0.18 mm

7. BEPD gives very narrow PSD of PP at 0.18 mm, EG gives broad at 1 mm

8. EG gives BD of 400, BEPD gives BD of 300

9. Optimum Mg/Ti is about 9

10. Optimum DOP/Ti is between 0.7 and 1.3

Examples 18 and 19

All the chemicals used were identical to the chemicals used in previous examples, except for the magnesium dichloride MgCl2.

Preparation of the Catalysts

The preparation of the catalysts was started by adding 1,2 g (12,6 mmol) of MgCl2, 2,1 g (13,1 mmol) BEPD and 8,2 ml (52,5 mmol) EHA to a glass reactor equipped with a magnetic stirrer. The mixture was heated up to 145 C. and mixed until a clear solution was obtained. The solution was cooled down and 2 ml of toluene was added.

Half of the solution was taken into a 50 ml glass reactor equipped with a stirrer. 18.0 ml (15.8 mmol) in example 18 and 16.0 ml (14 mmol) in example 19 of MgR2 (BOMAG-A) was added while the temperature was kept between 5 to 10 C. The temperature of the reaction solution was increased to 60 C. and 1.0 ml (7.0 mmol) of PDC was added. After the reaction was completed, 1.5 ml (14.3 mmol) BuCl was added. After 5 min the temperature was rised to 95-97 C. and about half of the liquid was evaporated with nitrogen stream. After evaporation 4.0 ml of toluene was added and the solution was then cooled down to room temperature.

This Mg complex solution was then added dropwise to 15.0 ml (136 mmol) of TiCl4 at 110 C. The components were allowed to react with each other for 15 min after which the solution was cooled down to 90 C. and 20 ml of toluene was added. After one hour, the formed precipitate was allowed to settle. When the settling step was complete the clear solution was siphoned off and the precipitate washed first once with toluene at 90 C., then twice with heptane at 90 C. Last, the catalyst was dried under a stream of nitrogen. The results are summarized in Table 28.

TABLE 28
Catalyst Example 18 Example 19
Mg (wt-%) 12.4 14.3
Ti (wt%) 5.4 2.3
DOP (wt-%) 24.1 29.5
DEP (wt-%w-%)
Activ. (kg PP/g cat) 23.4 16.4
BD (kg/m3) 430 420
MFR2 (g/10 min) 5.6 5.9
XS (wt-%) 2.6 3.8

Appendix 1. Two embodiments starting from MgX2

Appendix 2. Two embodiments starting from R2Mg

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
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Classifications
U.S. Classification526/123.1, 526/124.3, 526/348, 526/160, 526/348.6, 526/125.3, 502/116, 526/351, 502/152, 526/124.5, 502/125, 526/126
International ClassificationC08F4/654, C08F110/06, C08F10/00, C08F4/651
Cooperative ClassificationC08F4/6548, C08F110/06, C08F4/6543, C08F4/651
European ClassificationC08F110/06, C08F4/654K, C08F4/654D, C08F4/651
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